Edward c



UNITED STATES PATENT OFFICE.

EDWARD C. I-IOLTON OF OLMSTED FALLS, OHIO, ASSIGNOR TO' THE SHERWIN- WILLIAMS COMPANY, OF CLEVELAND, OHIO, A CORPORATION OF OHIO.

-METHOD OF TREATING POLYSULFID SOLUTIONS.

No Drawing. Original No. 1,254,908, dated. January 29, 1,918, Serial No. 64,477, filed December Application for reissue filed December To all iuhom it may concern:

Be it known that I, EDWARD (J. HoL'roN, a citizen of the United States, and a resident of Olmsted Falls, county of Uuyahoga, and,

State of Ohio, have invented a new and useful Improvement in Methods of Treat ng Polysulfid Solutions, of which the followlng is a specification, the principle of the inven tion being herein explained and the best mode inwhich I have contemplated applying that principle, so as to distinguish 1t from other inventions. v

The present invention relates to a new and improved composition having insectlcldal, fungicidal and fertilizer properties, and also to a method of producing such composition. The invention deals with polysulfids and particularly with calcium polysulfids. It is of courseknown that polysulfids of calcium are produced by on mono sulfids, oxids and hydroxids'of calcium under suitable conditions, and it is known thatwhen lime sulfur is produced by boiling lime in water with sulfur, the polysulfid which is formed is chiefly the tetrasulfid ofcalcium, but when calcium sulfhydrate is boiled in water .with sulfur the product is chiefly the pentasulfid of calcium. These polysulfids have been found to crystalize with a number of molecules of water as indicated by the formulas,-

Theresult of this crystallized water inthe polysulfids is to render them very unstable in the air and to cause decomposition into sulfur and other substances which are Very sparingly soluble in water. It is for the purpose of producing polysulfids which will be stable and which while in the dry state,

Wlll not decompose that the present invention has been designed. To the accomplishment of the foregoing and related ends, said invention, then, hereinafter fully described and-particularly pointed out in the claims.

The following description sets forth in detail one approved method of carrying out the invention, such disclosed mode, however, constituting but one of the various ways in which the principle ofthe invention niaybe used.

the, action of sulfur consists of the method Specification of Reissued Letters Patent. Reissued June 22,- 1920.

6, 1919. Serial No. 343,092.

My improved method comprises the following steps. To' a suitable solution of polysulfid, preferably having a specific gravity of practically 35 add a suitable water soluble substance in small amount, preferably from 1 to 5% of the weight of the polysulfid in solution. There are a'number of substances which may be used for this purpose and which will have no deleterious action on the polysulfid and yet will have the stabilizing influence that is desired and among such substances are cane sugar saccharoses, glucoses, maltoses, dextarin' and other soluble carbohydrates and the soluble substances formed Among these various subto 40 Bauln, I r

stances which. maybe used, cane sugar would preferably be employed in many cases as it exerts the necessary stabilizing and reinforcing effect on the polysulfid and has no deleterious action whatever, either on the nature of the polysulfid or on the use to which the final product is to be put.

This polysulfid solution to which cane sugar or another suitable water soluble substance has been added, is then evaporated to dryness, preferably under pressure lower.

by any desired process,

than atmospheric, although one giving very good results consists in exposing the mixture of polysulfid and cane sugar on a heated surface in a very thin layer and for time, preferabl atmospheric. he substance which then results from this evaporation is a mixture. of polysulfids and cane sugar with almost no a very short space of under pressure lower thanwater of crystallization in the polysulfid which has been reinforced the presence of the cane sugar. I

The final step in the process consists in "finely pulverizlng or grinding the dried product of the foregoing steps, thus producing a very fine powder which possesses very good insecticidal, fungicidal. and fertilizing properties which 1s almost completelysoluble in water'and of which the only parts that are not soluble have very good suspension qualities so that this prod.

and stabilized by not is very welladapted for use as a spraying material,

Other forms may be employed embodying the features of my invention instead of the one here explained, change being made in the form of construction, provided the elements stated by any of the following claims or the equivalent of such stated elements be employed, whether produced by method or by others embodying steps equivalent to those stated in the following claims.

I therefore particularly point out and distinctly claim as my invention 1. An insecticide comprising essentially dry calcium polysulfid containing a much smaller percentage of a substance formed by the combination of a water-soluble carbohydrate and a polysulfid of an alkaline earth metal.

2. An insecticide, comprising a relatively large percentage of polysulfid of an alkaline earth metal and relatively small percentage of a carbon compound including an alkaline earth compound in its composition, said insecticide being substantially dry, relatively stable on storage, readily miscible with water to form lime sulfur solution and having the particles of lime sulfur intimately and homogeneously incorporated with such carbon compound.

8. An insecticide, consisting essentially of calcium polysulfid and containing a minor percentage of a Water-soluble carbohydrate, said insecticide existing. in the form of a fine dry powder and possessing insecticidal, fungicidal and fertilizing value, being almostvcompletely soluble in water and hav-' ing the water-insoluble ingredients thereof readily suspensible in water, said insecticide being adapted for use with water as a spraying material.

4. The method of producing a dry, stable polysulfid of an alkaline earth metal, having high insecticidal value, which consists in forming a solution the solid content of which comprises a major percentage of a polysulfid of an alkaline earth metal and a minor percentagexof a water-soluble carbon compound which is capable of exerting in forming a solution the a stabilizing influence upon the polysulfid when reduced to a dry state and then rapidly evaporizing the mixture in oacuo to a suflicient degree of dryness to produce a dry, stable, water-soluble product containing considerably less water of crystallization than is represented by the formula polysulfid of an alkaline earth metal, hav ing high insecticidal value, which consists solid content of which comprises a major polysulfid of an alkaline earth metal and a minor percentage of a water-soluble carbon compound including an alkaline earth comv produce a dry,

my preferred percentage of a pound in its composition, which is capable of exerting a stabilizing influence upon the polysulfid when reduced to a dry state and then rapidly evaporating the mixturew'n cacao to, a suflicient degree of dryness to stable, water-soluble product containing considerably less water of crystallization than represented by the formula CaS,.9H O.

6. The method of producing a dry, stable polysulfid of an alkaline earth metal, having high insecticidal value, which consists in forming a solution the solid content of which comprises a major percentage of a polysulfid of an alkaline earth metal and a minor percentage. of carbon compound adapted to serve in a protective capacity and prevent decomposition of said polysulfid and then rapidly evaporating the mixture in 'vacuo to a suflicient degree of dryness to produce a dry, stable, watersoluble compound containing considerably less Water of crystallization than is reprepolysulfid of an alkaline earth metal, having high insecticidal value, which'consists in forming a solution the solid content of which comprises -a major percentage of a polysulfid of an alkaline earth metal and a minor percentage of a water-soluble carbohydrate compound which has no deleterious action on such polysulfid and is capable of exerting a stabilizing influence upon the polysulfid when reduced to a dry state and then rapidly evaporating the mixture in 'vacuo to a sufficient degree of dryness to produce a dry, stable, water-solubleproduct containing considerably less water of crystallization than is represented by the formula CaS,.9H O. I

8. The method of producing a dry, stable polysulfid of an alkaline earth metal, having high insecticidal value, which consists in forming a solution which comprises a major percentage of 'polysulfid of an alkaline earth metal and a minor percentage of a Water-soluble sugar which is capable of exerting a stabilizing influence upon the polysulfid when reduced to a dry state and then rapidly evaporating the mixture in 'vacuo to a suflicient degree of dryness to produce a dry, stable, watersoluble product containin considerably less water of crystallization than is represented by the formula CaS,.9H O.

9. In a method of stabilizing polysulfids, the step pared polysulfid solution .of specific gravity of -35-40. Baum or equivalent, of cane sugar in an amount equal to from one to five per cent., of the weight of polysulfid solution. v

10. In a method of s'tabilizinn polysulfids,

the steps which consist in addition to a prethe solid content of which consists in addition to a pre pared polysulfid solution of 3540 Baum, or equivalent, of cane sugar in an amount equal from one to five per cent. of weight of the-solution, rapidly evaporating such solution to dryness, and then pulverizing the dried product.

11. An insecticidal compound comprising lime sulfur and cane sugar in the proportions of approximately eight to one.

12. In a method of stabilizing polysulfids, 10 the'step which consists in the addition to a prepared polysulfid solution of a substance. formed by combining a Water-soluble carbohydrate with an alkaline earth metal.

Signed at the city of Cleveland, county 15.

of (luyahoga, State of Ohio, this 3rd of December, 1919. v

EDWARD C. HOLTON. 

